CN102618758B - Cast magnesium alloy of low linear shrinkage - Google Patents

Cast magnesium alloy of low linear shrinkage Download PDF

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CN102618758B
CN102618758B CN201210107721.3A CN201210107721A CN102618758B CN 102618758 B CN102618758 B CN 102618758B CN 201210107721 A CN201210107721 A CN 201210107721A CN 102618758 B CN102618758 B CN 102618758B
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magnesium alloy
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CN102618758A (en
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冯俊
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Jiaxing Jiasi Beite New Material Co Ltd
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Jianghan University
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Abstract

The invention discloses a cast magnesium alloy of low linear shrinkage, which belongs to the field of magnesium alloys. The magnesium alloy consists of Mg, Al, Zn, Mn, rare earth, Nb, Li and M element, wherein the materials have the following weight percentage composition: 1.5-25 percent of Al, 0.1-3.5 percent of Zn, 0.1-2.2 percent of Mn, 0.0002-16 percent of rare earth, 0.0002-4 percent of Nb, 0.0002-9 percent of Li, 0.0002-2 percent of M element and the balance Mg; and the M element is at least one of Zr, Ti, Sr, Ca, C and B. According to the heat-resistant magnesium alloy, the rare earth element and the Nb element are added into the magnesium alloy, so that the structure of beta phase is changed; the Zr element and the M element are added to refine crystal grains; due to combined action of the elements, latent heat of crystallization during alloy solidification is changed; and the magnesium alloy which has superior mold-filling capacity, low shrinkage, superior mechanical property and good machinability, fluidity and die-cast performance and is suitable for casting is obtained.

Description

A kind of low linear shrinkage ratio cast magnesium alloys
Technical field
The present invention relates to a kind of magnesium alloy, particularly a kind of applicable cast form, the high-performance magnesium-alloy of especially applicable Hpdc.
Background technology
Along with scientific and technological development, the vehicles that the automobile of take is representative need to, by alleviating the weight of vehicle body, further be researched and developed the product innovation that fuel availability is higher.In automobile industry, magnesium alloy, as a kind of novel lightweight metal material, is used for substituting traditional cast iron by automaker, to realize the object that alleviates tare.
At present, domestic MgAlZn is that the diecast magnesium alloy trade mark has YM302, YM303, YM304, YM305; The MgAlZn of USS ASTM B is that the diecast magnesium alloy trade mark has AZ91A, AZ91B, AZ91D; The MgAlZn of Nippon Standard JIS H is that the diecast magnesium alloy trade mark has MDC1B, MDC1D; The MgAlZn of European standard EN is that the diecast magnesium alloy trade mark has EN-MC21110, EN-MC21120, EN-MC21121.The alloy of these trades mark has all very good features of mobility, machinability, die casting performance, is widely used in the cast forms such as permanent mold casting, precision casting, low-pressure casting, die casting, semi-solid casting, sand mold casting.
In realizing process of the present invention, contriver finds that prior art at least exists following problem: magnesium alloy is when casting, molten metal is in being frozen into the process of solid, be subject to the impact of volume or linear shrinkage, internal stress is very large, easily cause the inner shrinkage porosite of foundry goods and surface cracking, the phenomenon that foundry goods die sinking ruptures even occurs.The impact that this decrepitation is serious the application of cast magnesium alloys, have influence on the qualification rate of magnesium alloy member.Above-mentioned diecast magnesium alloy linear shrinkage ratio is 1.5-2%, has obvious decrepitation, has limited its use range.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the embodiment of the present invention provides a kind of low linear shrinkage ratio cast magnesium alloys.Described technical scheme is as follows:
A kind of low linear shrinkage ratio cast magnesium alloys, described magnesium alloy is elementary composition by Mg, Al, Zn, Mn, rare earth, Nb, Li and M, its weight percent consists of Al 1.5-25%, Zn 0.1-3.5%, Mn 0.1-2.2%, rare earth 0.0002-16%, Nb0.0002-4%, Li 0.0002-9%, M element 0.0002-2%, and all the other are Mg; Wherein, M element is at least one in Zr, Ti, Sr, Ca, C, B.
Wherein, described rare earth is at least one in Gd, Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
Preferably, described rare earth is at least one in Gd or Gd and Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
Preferably, its weight percent consists of Al 1.5-2.5%, Zn 0.3-1%, Mn 0.1-0.6%, Gd 0.1-4%, Nb 0.05-1%, Li 0.001-9%, M element 0.001-2%, and all the other are Mg.
Preferably, its weight percent consists of Al 4.5-10%, Zn 0.3-1%, Mn 0.1-0.6%, Gd 0.1-2%, Nb 0.05-1%, Li 0.05-9%, M element 0.05-1%, and all the other are Mg.
More preferably, its weight percent consists of Al 7-9.7%, Zn 0.35-1%, Mn 0.12-0.6%, Gd 0.1-0.8%, Nb0.05-0.6%, Li 0.001-4%, M element 0.08-0.2%, and all the other are Mg.
Most preferably, its weight percent consists of Al 8.5%, Zn 0.5%, Mn 0.3%, rare earth 0.6%, Nb 0.2%, Li 2%, M element 0.1%, and all the other are Mg.
Wherein, described Nb adds described magnesium alloy by the form of AlNb master alloy or NbAl master alloy.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is: RE can form MgRE compound with Mg, Nb can form some resistant to elevated temperatures metallic compounds with other elements (as Al), Li and the acting in conjunction of M element, can strong crystal grain thinning and purification aluminium alloy.Combined action due to above-mentioned element, the particularly effect of Li element, while making alloy graining, latent heat changes, under the heat absorption of above-mentioned element, heat release combined action, it is diecast magnesium alloy that the time that aluminium alloy provided by the invention keeps liquid in mould is obviously longer than existing AZ, make alloy in process of setting, feeding is abundant, built-in thermal stress is little, heat crack resistance is good, simultaneously, because magnesium alloy liquid volume and solid-state volume variation that the embodiment of the present invention provides are very little, therefore there is the feature that cavity filling ability is good, shrinking percentage is low.The characteristics such as alloy of the present invention also has good mechanical property, and machinability, mobility and die casting are good.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
Manufacture craft, the heat treating method of the magnesium alloy that the embodiment of the present invention provides are described as follows:
1, the magnesium alloy that the embodiment of the present invention provides can be made by following three kinds of melting technologies:
Technique one: the magnesium alloy providing according to the embodiment of the present invention forms and content alloyage, in resistance furnace, add magnesium ingot, aluminium ingot, zinc ingot metal, MgMn master alloy and AlNb master alloy or NbAl master alloy, in addition, also add at least one in MgZr master alloy, AlTi master alloy, MgSr master alloy or AlSr master alloy, MgCa master alloy, Graphite Powder 99, AlB master alloy.Heat up to resistance furnace used, when the above-mentioned metal adding melts soon, adopt argon shield or magnesium alloy covering agent protection.While being warmed up to 720 ℃-780 ℃, add MgRE master alloy (as MgGd, MgY, MgNd etc.) or AlRE master alloy, AlLi master alloy or MgLi master alloy, and stir, 720 ℃ of-780 ℃ of standing insulations 30 minutes, obtain aluminium alloy.With gained aluminium alloy, water a fritter sample, detect its Melting Quality, as: according to gas content inspection method, carry out gas content inspection, if second-rate, need carry out refining treatment; If up-to-standard, described aluminium alloy temperature adjustment to 700 ℃-740 ℃ is skimmed, then pour into a mould, obtain the foundry goods of alloy of the present invention.
In this technique, resistance furnace also can replace with other smelting furnaces; Magnesium alloy covering agent and master alloy product are market sale product; Refining treatment method adopts the ordinary method of the industry.
Technique two: the magnesium alloy providing according to the embodiment of the present invention forms and content alloyage, in vacuum oven, add aluminium ingot, zinc ingot metal, AlMn master alloy, AlNb master alloy or NbAl master alloy, in addition, also add at least one in MgZr master alloy, AlTi master alloy, MgSr master alloy or AlSr master alloy, MgCa master alloy, Graphite Powder 99, AlB master alloy.Be warming up to 820 ℃, insulation 2-8 hour, then cools to 720 ℃-780 ℃, adds magnesium ingot, RE and AlLi master alloy or MgLi master alloy.After added melting of metal, 720 ℃-780 ℃ insulations 30 minutes, obtain aluminium alloy, adopt argon shield or magnesium alloy covering agent protection to prevent aluminium alloy oxidation.With gained aluminium alloy, water a fritter sample, detect its Melting Quality, as: the inspection of gas content, if second-rate, need carry out refining treatment; If up-to-standard, described aluminium alloy temperature adjustment to 700 ℃-740 ℃ is skimmed, then pour into a mould, obtain the foundry goods of alloy of the present invention.
In this technique, vacuum oven can substitute with other smelting furnaces such as main frequency furnaces; Magnesium alloy covering agent, RE and master alloy are sell goods on market; Refining treatment method adopts the ordinary method of the industry.
Technique three: the magnesium alloy providing according to the embodiment of the present invention forms and content alloyage, in smelting furnace, adding standard brand MgAlZn is diecast magnesium alloy, AlNb master alloy or NbAl master alloy, in addition, also add at least one in MgZr master alloy, AlTi master alloy, MgSr master alloy or AlSr master alloy, MgCa master alloy, Graphite Powder 99, AlB master alloy.Above-mentioned metal adopts argon shield or magnesium alloy covering agent protection while melting soon.While being warmed up to 720 ℃-780 ℃, add MgRE master alloy (as MgGd, MgY, MgNd etc.) or AlRE master alloy, AlLi master alloy or MgLi master alloy, and stir, 720 ℃ of-780 ℃ of standing insulations 30 minutes, obtain aluminium alloy.With gained aluminium alloy, water a fritter sample, detect its Melting Quality, as: according to gas content inspection method, carry out gas content inspection, if second-rate, need carry out refining treatment; If up-to-standard, described aluminium alloy temperature adjustment to 700 ℃-740 ℃ is skimmed, then pour into a mould, obtain the foundry goods of alloy of the present invention.
In this technique, magnesium alloy covering agent, RE and master alloy are sell goods on market; Refining treatment method adopts the ordinary method of the industry.
Thermal treatment and the treatment process thereof of the magnesium alloy that 2, the embodiment of the present invention provides:
Die casting in the magnesium alloy that the embodiment of the present invention provides can not heat-treated, and the cast member of other form can be heat-treated, and generally adopts T4 solution treatment.T4 solid solution treatment process is: cast member is warming up in chamber type electric resistance furnace to 410 ℃, argon shield, is incubated 12 hours, cast member come out of the stove after shrend, 40 ℃ of water temperatures.
Be subject to fusion process to select the impact of some other inevitable factor in the purity of raw material and melting, castingprocesses, the diecast magnesium alloy that the embodiment of the present invention provides may contain inevitable impurity, as Fe, Cu, Be etc., as long as described impurity does not cause obvious impact to the performance of magnesium alloy, and total impurities is controlled at the weight percent < 0.5% in described magnesium alloy finished product, in the weight percent < 0.1% of single contaminant in described magnesium alloy finished product, exist trace impurity also to allow.
Embodiment 1
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts die cast, the weight percent of described magnesium alloy consists of Al 1.5%, Zn 0.1%, Mn 0.1%, Y 0.0002%, Nb 0.0002%, Li 0.0002%, Zr 0.0002%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 2
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts semi-solid casting, and the weight percent of described magnesium alloy consists of Al 25%, Zn 3.5%, Mn 2.2%, Sc 16%, Nb 4%, Li 9%, Ti 2%, and all the other are Mg.
Foundry goods is heat-treated.The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 3
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of magnesium alloy consists of Al1.5%, Zn 0.3%, Mn 0.1%, Sm 0.1%, Nb 0.05%, Li 0.001%, Sr 0.001%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 4
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts low-pressure casting, and the weight percent of described magnesium alloy consists of Al 2.5%, Zn 1%, Mn 0.6%, Nd 4%, Nb 1%, Li 9%, Ca 2%, and all the other are Mg.
Foundry goods is heat-treated.The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 5
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts precision casting, and the weight percent of described magnesium alloy consists of Al 4.5%, Zn 0.3%, Mn 0.1%, La 0.1%, Nb 0.05%, Li 0.05%, C 0.05%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 6
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts sand mold casting, and the weight percent of described magnesium alloy consists of Al 10%, Zn 1%, Mn 0.6%, Ce 2%, Nb 1%, Li 9%, B 1%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 7
By step described in above-mentioned technique three, prepare magnesium alloy, the described standard brand diecast magnesium alloy using in preparation process is YM302, foundry goods adopts Hpdc, the weight percent of described magnesium alloy consists of Al 7%, Zn 0.45%, Mn 0.15%, Tb0.1%, Nb 0.05%, Li 0.05%, Bi 0.08%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 8
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Al 9.7%, Zn 1%, Mn 0.6%, Dy 0.8%, Nb 0.6%, Li 4%, Cd 0.2%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 9
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Al 8%, Zn 0.4%, Mn 0.4%, Gd 0.5%, Nb 0.3%, Li 1%, Ti 0.15%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 10
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, the weight percent of described magnesium alloy consists of Al 8%, Zn 0.4%, Mn 0.4%, Gd 0.3%, Ho 0.2%, Nb 0.3%, Li 1%, Ti 0.15%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 11
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Al 8%, Zn 0.4%, Mn 0.4%, Ho 0.5%, Nb 0.3%, Li 1%, Ti 0.15%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 12
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Al 3%, Zn 0.2%, Mn 2%, Er 10%, Nb 3%, Li 0.04%, Zr 1.5%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 13
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Al 20%, Zn 3%, Mn 1%, Gd 14%, Nb 2%, Li 0.02%, Sr 0.04%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 14
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Al 2%, Zn 0.35%, Mn 0.1%, Gd 3%, Nb 0.8%, Li 5%, Ca 0.8%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 15
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Al8.5%, Zn 0.5%, Mn 0.3%, Gd 0.6%, Nb 0.2%, Li 2%, Ti 0.1%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Comparative example 1
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Al8.5%, Zn 0.5%, Mn 0.3%, Gd 0.6%, Nb 0.2%, and all the other are Mg and inevitable impurity.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Comparative example 2
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Al8.5%, Zn 0.5%, Mn 0.3%, Gd 0.6%, Li 2%, Ti 0.1%, and all the other are Mg and inevitable impurity.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Comparative example 3
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Al8.5%, Zn 0.5%, Mn 0.3%, Gd 0.6%, and all the other are Mg and inevitable impurity.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
The Mg alloy castings that each embodiment provides above can contain micro-impurity, the weight percent < 0.5% of described inevitable total impurities in described magnesium alloy finished product, the weight percent < 0.1% of single contaminant in described magnesium alloy finished product.
Magnesium alloy provided by the invention is applicable to the forging types such as die cast, Hpdc, semi-solid casting, low-pressure casting, precision casting, sand mold casting.
The linear shrinkage ratio of the Mg alloy castings that various embodiments of the present invention and comparative example provide is referring to table 1.
The linear shrinkage ratio table of the Mg alloy castings that each embodiment of table 1 provides
As shown in Table 1, the linear shrinkage ratio of the magnesium alloying part that the embodiment of the present invention provides is all less than 1%, well below existing similar cast magnesium alloys, has good hot-cracking resistance; Simultaneously referring to embodiment 15 and comparative example 1-3, the Mg alloy castings that the embodiment of the present invention provides is compared with not adding Li or Nb or Mg alloy castings that both all do not add, has better hot-cracking resistance; By the contrast between embodiment 9-11, the known RE containing has the effect of Gd better; The linear shrinkage ratio of the Mg alloy castings that embodiment 15 provides is minimum, and the Mg alloy castings hot-cracking resistance that embodiment 15 provides is the strongest.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (7)

1. one kind low linear shrinkage ratio cast magnesium alloys, it is characterized in that, described magnesium alloy is elementary composition by Mg, Al, Zn, Mn, rare earth, Nb, Li and M, its weight percent consists of Al1.5-25%, Zn0.1-3.5%, Mn0.1-2.2%, rare earth 0.0002-16%, Nb0.0002-4%, Li0.0002-9%, M element 0.0002-2%, and all the other are Mg; Wherein, M element is at least one in Zr, Ti, Sr, Ca, C, B, described Nb adds in described magnesium alloy by the form of AlNb master alloy or NbAl master alloy, described Li adds in described magnesium alloy by the form of AlLi master alloy or MgLi master alloy, and the smelting temperature of the master alloy of described Nb is 720 ℃-780 ℃ or 820 ℃.
2. magnesium alloy according to claim 1, is characterized in that, described rare earth is at least one in Gd, Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
3. magnesium alloy according to claim 1 and 2, is characterized in that, described rare earth is at least one in Gd or Gd and Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
4. magnesium alloy according to claim 3, is characterized in that, its weight percent consists of Al1.5-2.5%, Zn0.3-1%, Mn0.1-0.6%, Gd0.1-4%, Nb0.05-1%, Li0.001-9%, M element 0.001-2%, and all the other are Mg.
5. magnesium alloy according to claim 3, is characterized in that, its weight percent consists of Al4.5-10%, Zn0.3-1%, Mn0.1-0.6%, Gd0.1-2%, Nb0.05-1%, Li0.05-9%, M element 0.05-1%, and all the other are Mg.
6. magnesium alloy according to claim 3, is characterized in that, its weight percent consists of Al7-9.7%, Zn0.35-1%, Mn0.12-0.6%, Gd0.1-0.8%, Nb0.05-0.6%, Li0.001-4%, M element 0.08-0.2%, and all the other are Mg.
7. according to right, want the magnesium alloy described in 1, it is characterized in that, its weight percent consists of Al8.5%, Zn0.5%, Mn0.3%, rare earth 0.6%, Nb0.2%, Li2%, M element 0.1%, and all the other are Mg.
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